Organic-inorganic hybrid material, fabrication process of the same and its starting material

ABSTRACT

An organic-inorganic hybrid material is disclosure. The organic-inorganic hybrid material contains 5˜50 wt % of inorganic compounds and has a characteristic peak at 1050±50 cm −1  in FTIR spectrum. Furthermore, the invention also provides a fabricating process of the organic-inorganic hybrid material as well as its starting material “isocyanates”. In particular, the isocyanates are prepared from carbonate containing compounds and amines.

CROSS-REFERENCE TO RELATED APPLICATION

This is a divisional application of U.S. patent application Ser. No.16/704,445 filed Dec. 5, 2019, which is incorporated by reference hereinin its entirety.

TECHNICAL FIELD OF THE INVENTION

The present invention relates to an organic-inorganic hybrid materialand its fabricating process as well as its starting material“isocyanates”. In particular, the organic-inorganic hybrid materialcontains 5˜50 wt % of inorganic compounds and has a characteristic peakat 1050±50 cm⁻¹ in FTIR spectrum.

BACKGROUND OF THE INVENTION

Composite materials, such as organic-inorganic hybrid materials andthermoset composites, are widely applied in the optical, electronic,medical device areas. The success of composites takes advantages fromthe fillers such as the inorganic particles or nature fibers with longor short length, and versatile polymers to tailored made propertiesrequired and required applications. However, these applications areusually hinged by the incompatibility between organic and inorganicmaterials since the phase separation caused by poor compatibilitybetween fillers and polymers.

Based on the aforementioned description, an organic-inorganic hybridmaterial and its fabricating process by using a novel additive arerequired for developing.

SUMMARY OF THE INVENTION

In one aspect, the present invention provides an organic-inorganichybrid material. The organic-inorganic hybrid material comprises aproduct produced from a sol-gel reaction of a composition, wherein theproduct comprises 5-50 wt % of inorganic compounds based on total weightof the product, and a structure of the organic-inorganic hybrid materialhas a characteristic peak at 1050±50 cm⁻¹ in FTIR spectrum.

In one aspect, the composition comprises a prepolymer and one selectedfrom the group consisting of a compound having a formula (1), a productprepared from an isocyanate and a phenolic compound, diphenyl carbonateand an inorganic bead.

In one aspect, the prepolymer comprises a polyurethane prepolymer, anepoxy oligomer or a polyamic acid. Preferably, the prepolymer hasmolecular weight between 5,000 and 50,000 Da.

In one aspect, the compound having a formula (1) is a modifier and itsfunction is to enhance compatibility of organic materials and inorganicmaterials.

The compound having a formula (1) is shown as following structure.

BP represents a polyphenol or a halogenated polyphenol; and X is(—CH₂-)_(m), or O and m is a integer of 1 to 10. Y is (H)_(a),(—OH)_(b), (—OCH₃)_(c), (—OCH₂CH₃)_(d) or (—OCH₂CH₂CH₃)_(e) and the sumof a, b, c, d and e is equal to 3. a, b, c, d, ore is a number of 0 to3.

In one aspect, the phenolic compound comprises 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxyphenyl) methane (bisphenol F), acompound having a formula (2), a compound having a formula (3) or acompound having a formula (4).

The compound having a formula (2) is shown as following structure.

The compound having a formula (3) is shown as following structure.

The compound having a formula (4) is shown as following structure.

R₁ independently represents a alkyl group with carbon numbers≤10, acycloalkyl group, a halogen substituted alkyl group, a carbonyl group, asulfonyl group, a sulfinyl group or a polyphenolic group.

R₂ independently represents H, a alkyl group with carbon numbers≤5, acycloalkyl group, a halogen substituted alkyl group, a carbonyl group, asulfonyl group, a sulfinyl group or a polyphenolic group.

Z is an integer of 1˜4; and p≤20.

In conclusion, the organic-inorganic hybrid material is prepared fromfour different formulations via the sol-gel reaction, respectively. Thefirst formulation comprises the compound having a formula (1) and theprepolymer. The second formulation comprises the product prepared fromthe isocyanates and phenolic compound and the prepolymer. The thirdformulation comprises diphenyl carbonate and the prepolymer, and thefourth formulation comprises the inorganic bead and the prepolymer.

In another aspect, the present invention discloses a process ofpreparation of the organic-inorganic hybrid material. The inventedprocess is able to use waste polycarbonate as a starting material andcarbon dioxide is not release in the invented process. Accordingly, theinvented process fixes carbon dioxide in the structure of theorganic-inorganic hybrid material, and prolongs carbon cycles. In brief,the invented process is an environmental-friendly process.

Typically, the process comprises following steps.

(I)Provides a compound having a formula (1), or a product prepared froma isocyanate and a phenolic compound, or diphenyl carbonate or ainorganic bead; (II)add the compound having a formula (1), or theproduct prepared from the isocyanate and the phenolic compound, ordiphenyl carbonate or the inorganic bead to a prepolymer havingmolecular weight between 5,000 and 50,000 Da to form a mixture, whereinthe mixture comprising 10-60 wt % of the prepolymer based on totalweight of the mixture; and (III) perform a sol-gel process to proceedthe mixture of an organic-inorganic hybrid material by hydrolysis andcondensation reaction, wherein the organic-inorganic hybrid materialcomprises 5-50 wt % of inorganic compounds based on its total weight,and structure of the organic-inorganic hybrid material has acharacteristic peak at 1050±50 cm⁻¹ in FTIR spectrum.

Generally, a solvent is required for making the mixture to form ahomogeneous phase. The solvent comprises tetrahydrofuran, dimethylsulfoxide, dimethylformamide, N-methyl-2-pyrrolidone or anisole.

The hydrolysis and condensation reaction is a hydrolytic condensationand performed at 20-60° C.

In still another aspect, the present invention provides a method ofpreparation of isocyanates from carbonate containing compounds.

The method of preparation of isocyanates from carbonate containingcompounds is a non-phosgene route. In particular, the method involvestwo heating stages for producing isocyanates. Carbon dioxide is notrelease from the heating stages. Furthermore, one of the carbonatecontaining compounds is waste polycarbonates, so the method can solvepollution problem caused by waste polymers.

The method of preparation of isocyanates from carbonate containingcompounds comprises following steps.

Provide a mixture comprises a carbonate containing compound, analiphatic amine or amino silane and a solvent, wherein the carbonatecontaining compound comprises polycarbonate, diphenyl carbonate or itsmixture, and perform a converting process to have the carbonatecontaining compound react with the aliphatic amine or amino silane toproduce isocyanates.

The converting process comprises a first heating stage and a secondheating stage, wherein the first heating stage operates at temperaturebetween 40 and 150° C., and the second heating stage operates attemperature between 100 and 250° C. under vacuum.

The vacuum pressure is 0.0001-400 mmHg.

Typically, concentration of the carbonate containing compound based ontotal weight of the mixture is 5-50 wt %.

According to the aforementioned invention content, the inventedorganic-inorganic hybrid material is produced from the compositioncomprises the modifier. The modifier significantly improves or increasesthe compatibility of the organic material and inorganic material, so asto enhance properties and/or performance of the inventedorganic-inorganic hybrid material, such as waterproof and filmformation. Secondly, the process of preparation of the inventedorganic-inorganic hybrid material is able to solve pollution problembecause a waste polymer, such as waste polycarbonate, is use as one ofthe starting materials in the process. Moreover, the invention providesa method for preparing isocyanates via a non-phosgene route. Carbondioxide is not release from the method. Hence, the method effectivelyprolongs carbon dioxide in carbon cycle.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a FTIR spectrum directed to the product prepared in experimentNo. 1;

FIG. 2 is a FTIR spectrum directed to the product prepared in experimentNo. 2;

FIG. 3 is a FTIR spectrum directed to the product prepared in experimentNo. 3;

FIG. 4 is a FTIR spectrum directed to the product prepared in experimentNo. 4;

FIG. 5 is a FTIR spectrum directed to the product prepared in experimentNo. 5; and

FIG. 6 is a FTIR spectrum directed to the product prepared in experimentNo. 10.

BRIEF DESCRIPTION OF THE PREFERRED EMBODIMENTS

In the first embodiment, the present invention discloses anorganic-inorganic hybrid material. The organic-inorganic hybrid materialcomprises a product produced from a sol-gel reaction of a composition,wherein the product comprises 5-50 wt % of inorganic compounds based ontotal weight of the product, and structure of the organic-inorganichybrid material has a characteristic peak at 1050±50 cm⁻¹ in FTIRspectrum.

The composition comprises a prepolymer and one selected from the groupconsisting of a compound having a formula (1), a product prepared froman isocyanate and a phenolic compound, diphenyl carbonate and aninorganic bead.

In one example of the first embodiment, the prepolymer comprises apolyurethane prepolymer, an epoxy oligomer or a polyamic acid. Thepolyamic acid is a precursor of polyimide.

In one example of the first embodiment, the prepolymer has molecularweight between 5,000 and 50,000 Da.

In one example of the first embodiment, the compound having a formula(1) is shown as following structure.

BP represents a polyphenol or a halogenated polyphenol; and X is(—CH₂-)_(m), or O and m is a integer of 1 to 10. Y is (H)_(a),(—OH)_(b), (—OCH₃)_(c), (—OCH₂CH₃)_(d) or (—OCH₂CH₂CH₃)_(e) and the sumof a, b, c, d and e is equal to 3. a, b, c, d, ore is a number of 0 to3.

The compound having a formula (1) is a modifier and its function is toenhance compatibility of organic materials and inorganic materials.

In an representative example of the first embodiment, the compoundhaving a formula (1) is(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl(3-(trimethoxy silyl)propyl)carbamate.

In one example of the first embodiment, the isocyanate comprises hexylisocyanate, octyl isocyanate, dodecyl isocyanate, octadecyl isocyanate,cyclohexyl isocyanate, trimethylsilyl isocyanate,3-(triethoxysilyl)propyl isocyanate, 3-(trimethoxysilyl)propylisocyanate, phenylethyl isocyanate, methyl isocyanate, ethyl isocyanate,propyl isocyanate, eicosyl isocyanate or tetracosyl isocyanate.

In one example of the first embodiment, the phenolic compound comprises2,2-bis(4-hydroxyphenyl) propane (bisphenol A), 2,2-bis(4-hydroxyphenyl)methane (bisphenol F), a compound having a formula (2), a compoundhaving a formula (3) or a compound having a formula (4).

The compound having a formula (2) is shown as following structure.

The compound having a formula (3) is shown as following structure.

The compound having a formula (4) is shown as following structure.

R₁ independently represents a alkyl group with carbon numbers≤10, acycloalkyl group, a halogen substituted alkyl group, a carbonyl group, asulfonyl group, a sulfinyl group or a polyphenolic group.

R₂ independently represents H, a alkyl group with carbon numbers≤5, acycloalkyl group, a halogen substituted alkyl group, a carbonyl group, asulfonyl group, a sulfinyl group or a polyphenolic group.

Z is an integer of 1˜4; and p≤20.

In one example of the first embodiment, the inorganic bead is producedby coating the compound having a formula (1), or the product preparedfrom the isocyanate and the phenolic compound onto a surface of aninorganic particle.

In one example of the first embodiment, the inorganic particle comprisessilicon oxide, silicon sulfide, aluminum oxide, aluminum sulfide,titanium oxide, titanium sulfide, germanium oxide, germanium sulfide,iron oxide, iron sulfide, barium oxide, barium sulfide, zinc oxide, zincsulfide, copper oxide, copper sulfide, chromium oxide, chromium sulfide,niobium oxide, niobium sulfide, manganese oxide, manganese sulfide, tinoxide, tin sulfide, lithium oxide, lithium sulfide, cerium oxide, ceriumsulfide, cobalt oxide, cobalt sulfide, SiO2, TiO2, ZnO, ZrO₂, Fe₂O₃,BaTiO₃, LiNbO₃, CdSe, CuO, BaZrO₃, Cr₂O₃, Nb₂O₅, CsO₂, FeTiO₃, FeS,mixture of Al₂O₃ and TiO₂, mixture of Al₂O₃ and ZrO₂, MnO₂, SnO or ZnS.

In one example of the first embodiment, the inorganic particle hasaverage diameters between 20 to 1,000 nm.

In one example of the first embodiment, the inorganic compounds areprepared by hydrolysis and condensation reaction. The hydrolysis andcondensation reaction is hydrolytic condensation.

In one example of the first embodiment, the inorganic compounds comprisesilicon oxide, silicon sulfide, aluminum oxide, aluminum sulfide,titanium oxide, titanium sulfide, germanium oxide, germanium sulfide,iron oxide, iron sulfide, barium oxide, barium sulfide, zinc oxide, zincsulfide, copper oxide, copper sulfide, chromium oxide, chromium sulfide,niobium oxide, niobium sulfide, manganese oxide, manganese sulfide, tinoxide, tin sulfide, lithium oxide, lithium sulfide, cerium oxide, ceriumsulfide, cobalt oxide, cobalt sulfide, SiO2, TiO2, ZnO, ZrO₂, Fe₂O₃,BaTiO₃, LiNbO₃, CdSe, CuO, BaZrO₃, Cr₂O₃, Nb₂O₅, CsO₂, FeTiO₃, FeS,mixture of Al₂O₃ and TiO₂, mixture of Al₂O₃ and ZrO₂, MnO₂, SnO or ZnS.

In the second embodiment, the invention discloses a process ofpreparation of the organic-inorganic hybrid material described in thefirst embodiment.

The process comprises following steps: (I)Provides a compound having aformula (1), or a product prepared from a isocyanate and a phenoliccompound, or diphenyl carbonate or a inorganic bead; (II)add thecompound having a formula (1), or the product prepared from theisocyanate and the phenolic compound, or diphenyl carbonate or theinorganic bead to a prepolymer having molecular weight between 5,000 and50,000 Da to form a mixture, wherein the mixture comprising 10-60 wt %of the prepolymer based on total weight of the mixture; and (III)perform a sol-gel process to proceed the mixture of an organic-inorganichybrid material by hydrolysis and condensation reaction, wherein theorganic-inorganic hybrid material comprises 5-50 wt % of inorganiccompounds based on its total weight, and structure of theorganic-inorganic hybrid material has a characteristic peak at 1050±50cm⁻¹ in FTIR spectrum.

In one example of the second embodiment, the compound having a formula(1) is shown as following structure.

BP represents a polyphenol or a halogenated polyphenol; and X is(—CH₂-)_(m), or O and m is a integer of 1 to 10. Y is (H)_(a),(—OH)_(b), (—OCH₃)_(c), (—OCH₂CH₃)_(d) or (—OCH₂CH₂CH₃)_(e) and the sumof a, b, c, d and e is equal to 3. a, b, c, d, ore is a number of 0 to3.

The compound having a formula (1) is a modifier and its function is toenhance compatibility of organic materials and inorganic materials.

In an representative example of the second embodiment, the compoundhaving a formula (1) is(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)carbamate.

In one example of the second embodiment, the isocyanate comprises hexylisocyanate, octyl isocyanate, dodecyl isocyanate, octadecyl isocyanate,cyclohexyl isocyanate, trimethylsilyl isocyanate,3-(triethoxysilyl)propyl isocyanate, 3-(trimethoxysilyl)propylisocyanate, phenylethyl isocyanate, methyl isocyanate, ethyl isocyanate,propyl isocyanate, eicosyl isocyanate or tetracosyl isocyanate.

In one example of the second embodiment, the phenolic compound comprises2,2-bis(4-hydroxyphenyl) propane (bisphenol A), 2,2-bis(4-hydroxyphenyl)methane (bisphenol F), a compound having a formula (2), a compoundhaving a formula (3) or a compound having a formula (4).

The compound having a formula (2) is shown as following structure.

The compound having a formula (3) is shown as following structure.

The compound having a formula (4) is shown as following structure.

R₁ independently represents a alkyl group with carbon numbers≤10, acycloalkyl group, a halogen substituted alkyl group, a carbonyl group, asulfonyl group, a sulfinyl group or a polyphenolic group.

R₂ independently represents H, a alkyl group with carbon numbers≤5, acycloalkyl group, a halogen substituted alkyl group, a carbonyl group, asulfonyl group, a sulfinyl group or a polyphenolic group.

Z is an integer of 1-4; and p≤20.

In one example of the second embodiment, the inorganic bead is producedby coating the compound having a formula (1), or the product preparedfrom the isocyanate and the phenolic compound onto a surface of aninorganic particle.

In one example of the second embodiment, the inorganic particlecomprises silicon oxide, silicon sulfide, aluminum oxide, aluminumsulfide, titanium oxide, titanium sulfide, germanium oxide, germaniumsulfide, iron oxide, iron sulfide, barium oxide, barium sulfide, zincoxide, zinc sulfide, copper oxide, copper sulfide, chromium oxide,chromium sulfide, niobium oxide, niobium sulfide, manganese oxide,manganese sulfide, tin oxide, tin sulfide, lithium oxide, lithiumsulfide, cerium oxide, cerium sulfide, cobalt oxide, cobalt sulfide,SiO2, TiO₂, ZnO, ZrO₂, Fe₂O₃, BaTiO₃, LiNbO₃, CdSe, CuO, BaZrO₃, Cr₂O₃,Nb₂O₅, CsO₂, FeTiO₃, FeS, mixture of Al₂O₃ and TiO₂, mixture of Al₂O₃and ZrO₂, MnO₂, SnO or ZnS.

In one example of the second embodiment, the inorganic particle hasaverage diameters between 20 to 1,000 nm.

In one example of the second embodiment, the prepolymer comprises apolyurethane prepolymer, an epoxy oligomer or a polyamic acid.

In one example of the second embodiment, the mixture further comprises asolvent, an additive or its combination. Preferably, the solventcomprises tetrahydrofuran, dimethyl sulfoxide, dimethylformamide,N-methyl-2-pyrrolidone or anisole.

In one example of the second embodiment, the additive comprises boricacid, phosphoric acid, hydrochloride acid, sulfuric acid, nitric acid,acetic acid, formic acid, propionic acid, alkali metal hydroxide, sodiumphosphate, aliphatic amine, piperidine and its derivatives, imidazoleand its derivatives or nitrogen heterocyclic compounds.

In one example of the second embodiment, the hydrolysis and condensationreaction is performed at a temperature between 20 and 60° C.

In a third embodiment, the invention provides a method for preparationof isocyanates from carbonate containing compounds.

The method comprises following steps: provide a mixture comprises acarbonate containing compound, an aliphatic amine or amino silane and asolvent, wherein the carbonate containing compound comprisespolycarbonate, diphenyl carbonate or its mixture; and perform aconverting process to have the carbonate containing compound react withthe aliphatic amine or amino silane to produce isocyanates.

In one example of the third embodiment, the converting process comprisesa first heating stage and a second heating stage, wherein the firstheating stage operates at temperature between 40 and 150° C., and thesecond heating stage operates at temperature between 100 and 250° C.under vacuum. Preferably, the vacuum pressure is 0.0001-400 mmHg

In one example of the third embodiment, the aliphatic amine comprisesbenzylamine, ethylamine, phenethylamine, propylamine,3-phenylpropylamine, butylamine, 4-phenylbutylamine, pentylamine,5-phenylpentylamine, hexylamine, 6-phenylhexylamine, isobutylamine,aminoethylpiperazine, 1-methylpiperazine, 3-morpholinopropylamine oraminoethylpiperazine.

In one example of the third embodiment, the amino silane comprises(3-aminopropyl)triethoxysilane or (3-aminopropyl)trimethoxysilane.

In one example of the third embodiment, the mixture comprises 5-50 wt %of the carbonate containing compound based on total weight of themixture.

In one example of the third embodiment, the solvent comprises diethylether, di-n-propyl ether, isopropyl ether, anisole, ethoxybenzene,propoxybenzene, butoxybenzene, 2-methoxytoluene, 3-methoxytoluene,4-methoxytoluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether,tetrahydrofuran, 2,3-dihydropyran, tetrahydropyran, 2-methyltetrahydropyran, benzene, toluene, xylene, ethylbenzene, diethylbenzeneor cyclohexylbenzene.

Representative examples of the invention are described as the followingparagraphs.

General Procedure for Preparing the Compound Having a Formula (1)

Isocyanates and phenolic compounds are dissolved in a non-polar solventto form a mixture. Preferably, the mixture is a homogenous mixture. Heatthe mixture to 60˜100° C. for performing reaction of the isocyanates andphenolic compounds. Some catalysts, such as organic tin compound,organic zinc compound or amines, are added into the mixture to speed upthe reaction. The reaction is monitored by FTIR. When the reaction iscompleted, remove the non-polar solvent and then purify the product bydistillation or column chromatography to obtain the compound having aformula (1).

Representative Example of the Compound Having a Formula (1):(4-(2-(4-Hydroxyphenyl)Propan-2-Yl)Phenyl(3-(Trimethoxysilyl)Propyl)Carbamate

3-(Triethoxysilyl)propyl isocyanate (5.0 g) and bisphenol-A (3.69 g) aredissolved in toluene (50 ml) to form a reaction mixture. Heat thereaction mixture to 80˜100° C. and add an organic tin compound as acatalyst. Bisphenol A is monitored by thin layer chromatography andtotally consumed after 12 hours. The crude product is purified andremoved toluene. FTIR is used to monitor functional grouptransformation. When a peak at about 1716 cm⁻¹ is observed, it means acompound having carbamate group is produced. Finally,(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)carbamate (7.8 g) is obtained and furtheridentified by FTIR and ¹H-NMR.

FTIR(KBr):1716 cm⁻¹, 3350 cm⁻¹ (NH, urethane), 950 cm⁻¹ (Si—O); ¹H-NMR(400 MHz, d-DMSO): δ(ppm)=0.5 (t, 6H), 1.2 (t, 27H), 1.5 (t, 18H), 3.0(m, 6H), 3.8 (m, 18H), 6.7 (m, 6H), 7.0 (m, 12H), 7.2 (m, 6H), 7.7 (t,3H), 9.2 (s, 3H).

The isocyanates used in the general procedure for preparing the compoundhaving a formula (1) further comprises hexyl isocyanate, octylisocyanate, dodecyl isocyanate, octadecyl isocyanate, cyclohexylisocyanate, trimethylsilyl isocyanate, 3-(triethoxysilyl)propylisocyanate, 3-(trimethoxysilyl)propyl isocyanate, phenylethylisocyanate, methyl isocyanate, ethyl isocyanate, propyl isocyanate,eicosyl isocyanate or tetracosyl isocyanate.

The phenolic compounds used in the general procedure for preparing thecompound having a formula (1) further comprises 2,2-bis(4-hydroxyphenyl)methane (bisphenol F), the compound having a formula (2), the compoundhaving a formula (3) or the compound having a formula (4) that describedin the aforementioned embodiments.

General Procedure for Preparing the Inorganic Bead

The compound having a formula(1) condensates with a hydroxy group, anamino group or a thiol group on surface of the inorganic particle in amedium, so as to modify the surface of the inorganic particle. Aftercondensation reaction, the compound having a formula(1) has bond on thesurface of the inorganic particle to form the inorganic bead. Isolatethe inorganic bead from the medium by filtration and then dry it,finally, the inorganic bead is obtained. The inorganic bead is asurface-functionalized inorganic particle.

General Procedure for Preparing the Organic-Inorganic Hybrid Material

Provide the compound having a formula (1), or the product prepared fromthe isocyanates and phenolic compound, or diphenyl carbonate, or theinorganic bead. In particular, the compound having a formula (1), or theproduct prepared from the isocyanates and phenolic compound has acarbamate group in their structure, so as to possess very goodcompatibility with a polymer or prepolymer that has carbonyl group. Addthe compound having a formula (1), or the product prepared from theisocyanates and phenolic compound, or diphenyl carbonate, or theinorganic bead into a prepolymer that comprises polyurethane prepolymer,epoxy oligomer or a precursor of polyimide “polyamic acid” to form amixture, and use FTIR to analyze the mixture. The FTIR analysis shows apeak at 950 cm⁻¹ position (Si—O—R). Dilute the mixture with a solventand then add 0.1˜5 wt % of acid catalyst, such as HCl, HNO₃ or HOAc toform a reaction composition. Place the reaction composition into an ovenat 60° C. for performing sol gel reaction. After 24˜48 hours, the peakat 950 cm⁻¹ position disappears and the sol gel reaction is completed.At the same time, a new peak at 1000˜1100 cm⁻¹ position (Si—O—Si) inFTIR is observed. After removing the solvent and purification, theinvented organic-inorganic hybrid material is obtained.

General Procedure for Preparing the PU Prepolymer

The polyurethane (PU) prepolymer is prepared by polycondensation of theisocyanates and polyols. The isocyanates comprise IPDI or HDI and thepolyols comprises PEG, PTMEG, PCL or PCPO. The polycondensation isperformed at 60-80° C. Solvents including DMF, NMP, THF, DMSO or anisoleare added for increasing the reaction rate. After the polycondensationis finished, a characteristic peak of carbamate group is observed in theFTIR spectrum.

The PU prepolymers and the compound having a formula (1)((4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)carbamate) are used to prepare the inventedorganic-inorganic hybrid material according to the general proceduredescribed in paragraph [0098][0099], respectively. The experimentalresults are list in TABLE 1. CA represents water contact angle andsilica (%) represents the weight percentage of the inorganic compoundsin the invented organic-inorganic hybrid material. The value afterpolyols represents their molecular weight, for example, PTMEG 2000 is aPTMEG has molecular weight of 2,000 g/mol.

TABLE 1 Compositions (gram) Water Isocyanate Polyol Silica (%)⁾adsorption Film Experiment (mol) (mol) (wt %) CA⁾ (°) (wt %) quality No.1 MDI(1.05) PCL2000(4.2) 0 — — X No. 2 MDI(1.05) PCL2000(4.2) 4.4 81.18.6 ◯ No. 3 MDI(1.05) PCPO2000(4.2) 0 — — X No. 4 MDI(1.05)PCPO2000(4.2) 4.4 82.3 3.8 ⊚ No. 5 MDI(1.05) PTMEG2000(4.2) 0 — — X No.6 MDI(1.05) PTMEG2000(4.2) 4.4 79.1 gelation X No. 7 MDI(1.05)PTMEG2000(4.2) 13.0 83.2 10.7  ⊚ No. 8 MDI(1.05) PTMEG2000(4.2) 26.085.0 7.3 ⊚ No. 9 MDI(1.05) PTMEG2000(4.2) 36.0 86.6 5.6 ⊚ No. 10MDI(1.05) PTMEG2000(4.2) 49.0 85.7 4.2 ⊚ X represents poor film quality;◯ represents good film quality; ⊚ represents excellent film quality

Experiment No. 1, No. 3 and No. 5 are control group and not added thecompound having a formula (1), respectively. As shown FIG. 1 , the FTIRspectrum show a peak at 1737 cm⁻¹ which is a carbamate group formed byMDI and PCL 2000.

Experiment No. 2 is to add the compound having a formula(1) into the PUprepolymer prepared from MDI and PCL 2000 to form a mixture, dilute themixture with a proper solvent and add 0.1˜5 wt. % of acid catalyst.Allow the film formation in an oven at 60° C. The sol-gel reaction isfinished after 24˜48 hours, remove the solvent and use FTIR to monitorthe functional group transformation. The peak at 950 cm⁻¹ (Si—O—R)disappears and a new peak at 1041 cm⁻¹ (Si—O—Si) is observed. Afterpurification and drying, the organic-inorganic hybrid material preparedfrom the PU prepolymer and the compound having a formula (1) is obtainedand the FTIR spectrum is shown in FIG. 2 .

The FTIR spectrum of experiment No. 3 is shown in FIG. 3 . A peak at1742 cm⁻¹ is observed and it means carbamate functional group. Incomparison with experiment No. 4, the experiment No. 4 is theorganic-inorganic hybrid material prepared from the PU prepolymer formedby polycondensation of MDI and PCPO2000 and the compound having aformula (1). The FTIR spectrum as shown in FIG. 4 , a peak at 1085 cm⁻¹(Si—O—Si) is observed.

The FTIR spectrum of experiment No. 5 is shown in FIG. 5 . A peak at1732 cm⁻¹ is observed. In comparison with experiment No. 5, experimentNo. 10 is add the inorganic bead containing silica and having a size of20˜1,000 nm to the prepolymer formed by polycondensation of MDI andPTMEG2000 to form a mixture, dilute the mixture with a proper solventand add 0.1˜5 wt. % of acid catalyst. Allow the film formation in anoven at 60° C. The sol-gel reaction is finished after 24˜48 hours,remove the solvent and use FTIR to monitor the functional grouptransformation. The peak at 950 cm⁻¹ (Si—O—R) disappears and a new peakat 1095 cm⁻¹ (Si—O—Si) is observed. After purification and drying, theorganic-inorganic hybrid material prepared from the PU prepolymer andthe inorganic bead is obtained. The FTIR spectrum is shown in FIG. 6 .

According to the aforementioned experimental results, the compoundhaving a formula(1) or its modified inorganic bead effectively enhancethe properties of the organic-inorganic hybrid material, such aswaterproof property and film quality. The organic-inorganic hybridmaterial has water contact angle more than 80 degree and 5˜50% of theinorganic compounds. As a result, the organic-inorganic hybrid materialis good to construct waterproof devices or insulator.

Representative Example of the Isocyanates Prepared from the CarbonateContaining Compounds

(3-aminopropyl)trimethoxysilane (7.19 g) and polycarbonate (10.0 g) aremixed in a solvent to form a reaction mixture. The solvent comprisesdiethyl ether, di-n-propyl ether, isopropyl ether, anisole,ethoxybenzene, propoxybenzene, butoxybenzene, 2-methoxytoluene,3-methoxytoluene, 4-methoxytoluene, benzyl ethyl ether, diphenyl ether,dibenzyl ether, tetrahydrofuran, 2,3-dihydropyran, tetrahydropyran,2-methyl tetrahydropyran, benzene, toluene, xylene, ethylbenzene,diethylbenzene or cyclohexylbenzene. Firstly, heat the reaction mixtureto 80˜90° C. and keep temperature for 1 hour at least, and then raisethe temperature to 200˜250° C. for the second heating stage. The secondheating stage is operated under vacuum, and pressure is 0.0001-400 mmHg.Finally, a isocyanate derived from (3-aminopropyl)trimethoxysilane (5.12g) is obtained. The isocyanate derived from(3-aminopropyl)trimethoxysilane has a characteristic peak at 2260 cm⁻¹in FTIR spectrum.

The amino compound used in the aforementioned representative example ofisocyanates further comprises benzylamine, ethylamine, phenethylamine,propylamine, 3-phenylpropylamine, butylamine, 4-phenylbutylamine,pentylamine, 5-phenylpentylamine, hexylamine, 6-phenylhexylamine,isobutylamine, aminoethylpiperazine, 1-methylpiperazine,3-morpholinopropylamine, aminoethylpiperazine or(3-Aminopropyl)triethoxysilane.

Obviously many modifications and variations are possible in light of theabove teachings. It is therefore to be understood that within the scopeof the appended claims the present invention can be practiced otherwisethan as specifically described herein. Although specific embodimentshave been illustrated and described herein, it is obvious to thoseskilled in the art that many modifications of the present invention maybe made without departing from what is intended to be limited solely bythe appended claims.

What is claimed is:
 1. A product produced from a sol-gel reaction of acomposition, wherein the product is an organic-inorganic hybrid materialcomprising 5-50 wt % of inorganic compounds, based on total weight ofthe product, and a structure having a characteristic peak at 1050±50cm⁻¹ in FTIR spectrum; wherein the composition comprises a prepolymerand an inorganic bead; wherein the inorganic bead is an inorganicparticulate material of inorganic particles that have been surfacefunctionalized with a compound having a formula (1):

where BP represents a polyphenol or a halogenated polyphenol; X is(—CH₂—)m or O, and m is a integer of 1 to 10; Y is (H)_(a), (—OH)_(b),(—OCH₃)_(c), (—OCH₂CH₃)_(d) or (—OCH₂CH₂CH₃)_(e), where the sum of a, b,c, d, and e is equal to 3; and a, b, c, d, and e are each a number of 0to 3, provided that at least one of c, d, and e is a number of 1 to 3.2. The product produced from a sol-gel reaction of a compositionaccording to claim 1, wherein the compound having a formula (1) is4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)carbamate.3. The product produced from a sol-gel reaction of a compositionaccording to claim 1, wherein the inorganic particulate materialcomprises inorganic particles of silicon oxide, silicon sulfide,aluminum oxide, aluminum sulfide, titanium oxide, titanium sulfide,germanium oxide, germanium sulfide, iron oxide, iron sulfide, bariumoxide, barium sulfide, zinc oxide, zinc sulfide, copper oxide, coppersulfide, chromium oxide, chromium sulfide, niobium oxide, niobiumsulfide, manganese oxide, manganese sulfide, tin oxide, tin sulfide,lithium oxide, lithium sulfide, cerium oxide, cerium sulfide, cobaltoxide, cobalt sulfide, SiO₂, TiO₂, ZnO, ZrO₂, Fe₂O₃, BaTiO₃, LiNbO₃,CdSe, CuO, BaZrO₃, Cr₂O₃, Nb₂O₅, CsO₂, FeTiO₃d , FeS, mixture of Al₂O₃and TiO₂, mixture of Al₂O₃ and ZrO₂, MnO₂, SnO or ZnS.
 4. The productproduced from a sol-gel reaction of a composition according to claim 1,wherein the inorganic particulate material of inorganic particles hasaverage diameters between 20 to 1,000 nm.
 5. The product produced from asol-gel reaction of a composition according to claim 1, wherein theprepolymer comprises a polyurethane prepolymer, an epoxy oligomer or apolyamic acid.
 6. The product produced from a sol-gel reaction of acomposition according to claim 1, wherein the prepolymer has molecularweight between 5,000 and 50,000 Da.
 7. A process for preparation of aproduct comprising: (1) providing an inorganic bead; wherein theinorganic bead is an inorganic particulate material of inorganicparticles that have been surface functionalized with a compound having aformula (1)

where BP represents a polyphenol or a halogenated polyphenol; X is(—CH₂—)_(m) or O, and m is a integer of 1 to 10; Y is (H)_(a),(—OH)_(b), (—OCH₃)_(c), (—OCH₂CH₃)_(d) or (—OCH₂CH₂CH₃)_(e), and wherethe sum of a, b, c, d, and e is equal to 3; and a, b, c, d, and e areeach a number of 0 to 3, provided that at least one of c, d, and e is anumber of 1 to 3; (2) adding the inorganic bead to a prepolymer havingmolecular weight between 5,000 and 50,000 Da to form a mixture, whereinthe mixture comprises 10-60 wt % of the prepolymer, based on totalweight of the mixture; and (3) performing a sol-gel reaction of mixtureto produce the product; wherein the product is an organic-inorganichybrid material comprising 5-50 wt % of inorganic compounds, based ontotal weight of the product, and a structure having a characteristicpeak at 1050±50 cm⁻¹ in FTIR spectrum.
 8. The process according to claim7, wherein the compound having a formula (1) is4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)carbamate.9. The process according to claim 7, wherein the inorganic particulatematerial comprises inorganic particles of silicon oxide, siliconsulfide, aluminum oxide, aluminum sulfide, titanium oxide, titaniumsulfide, germanium oxide, germanium sulfide, iron oxide, iron sulfide,barium oxide, barium sulfide, zinc oxide, zinc sulfide, copper oxide,copper sulfide, chromium oxide, chromium sulfide, niobium oxide, niobiumsulfide, manganese oxide, manganese sulfide, tin oxide, tin sulfide,lithium oxide, lithium sulfide, cerium oxide, cerium sulfide, cobaltoxide, cobalt sulfide, SiO₂, TiO₂, ZnO, ZrO₂, Fe₂O₃, BaTiO₃, LiNbO₃,CdSe, CuO, BaZrO₃, Cr₂O₃, Nb₂O₅, CsO₂, FeTiO₃, FeS, mixture of Al₂O₃ andTiO₂, mixture of Al₂O₃ and ZrO₂, MnO₂, SnO or ZnS.
 10. The processaccording to claim 7, wherein the inorganic particulate material ofinorganic particles has an average diameter between 20 and 1,000 nm. 11.The process according to claim 7, wherein the prepolymer comprises apolyurethane prepolymer, an epoxy oligomer or a polyamic acid.
 12. Theprocess according to claim 7, wherein the mixture further comprises asolvent, an additive or its combination.
 13. The process according toclaim 12, wherein the solvent comprises tetrahydrofuran, dimethylsulfoxide, dimethylformamide, N-methyl-2-pyrrolidone or anisole.
 14. Theprocess according to claim 12, wherein the additive comprises boricacid, phosphoric acid, hydrochloride acid, sulfuric acid, nitric acid,acetic acid, formic acid, propionic acid, alkali metal hydroxide, sodiumphosphate, aliphatic amine, piperidine and its derivatives, imidazoleand its derivatives or nitrogen heterocyclic compounds.
 15. The processaccording to claim 7, wherein the sol-gel reaction is performed at atemperature between 20 and 60° C.